EP1308496B1 - Flüssigkeit für Getriebe mit veringerter Rostfrasskorrosion - Google Patents

Flüssigkeit für Getriebe mit veringerter Rostfrasskorrosion Download PDF

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Publication number
EP1308496B1
EP1308496B1 EP02257642A EP02257642A EP1308496B1 EP 1308496 B1 EP1308496 B1 EP 1308496B1 EP 02257642 A EP02257642 A EP 02257642A EP 02257642 A EP02257642 A EP 02257642A EP 1308496 B1 EP1308496 B1 EP 1308496B1
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Prior art keywords
fluid
percent
oils
acid
transmission
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French (fr)
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EP1308496A2 (de
EP1308496A3 (de
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J.L. Sumiejski
William C.Jr. Ward
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Lubrizol Corp
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Lubrizol Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present invention relates to the use of a compound to reduce metal pitting performance in a transmission fluid.
  • CVTs Continuously variable transmissions
  • a description of CVTs, including a popular variety, the push-belt CVT, and fluids suitable for use therein is found in U.S. Patent 5,750,477, Sumiejski et al., May 12, 1998.
  • Another device which may fall within the description of a CVT is a traction drive.
  • Traction drives are devices in which power or torque is transmitted from an input element to an output element through nominal point or line contact, typically with a rolling action, by virtue of the traction between the contacting elements.
  • Traction drives can be generally used in automotive or industrial machinery for transmitting power between rotating members. Traction fluids and traction drives in which they can be used have been described for instance, in U.S. Patents 4,693,134 and 5,043,497.
  • PCT Publication WO0070001 discloses high boron formulations for continuously variable transmissions.
  • metal deactivators such as tolyltriazole, benzotriazole, and the methylene-coupled product of tolyltriazole and amines such as 2-ethylhexylamine.
  • Such metal deactivators can be useful in adjusting the metal-to-metal friction in push belt CVTs.
  • European Patent Publication 761 805, March 12, 1997 discloses lubrication fluids for reduced air entrainment, using 2,5-dimercapto-1,3,4-thiadiazole to provide antiwear properties, along with certain antifoam agents.
  • the fluids can be continuously variable transmission fluids.
  • the oil has a kinematic viscosity of 2-10 cSt at 100°C and the composition has a Brookfield viscosity of less than 20,000 cP at -40°C.
  • European Patent Publication 987 311, March 22, 2000 discloses transmission fluid compositions, especially for continuously variable transmissions. Corrosion inhibitors can be included in the composition.
  • EP-A-976813 discloses an extreme pressure additive comprising (a) from 30% to 70% of an alkali-metal borate, preferably from 40% to 66% of potassium triborate; (b) from 10% to 30% of an organic polysulfide, preferably from 12% to 25% of a di-tertiary-butyl-trisulfide; (c) from 1% to 20% of an alkyl succinic acid ester of a polyol, preferably from 5% to 15% of the reaction product of pentaerythritol and poly-isobutenyl succinic anhydride; and (d) from 0.5% to 20% of an overbased sulfurized alkyl or alkenyl salicylate, preferably from 5% to 10% of an overbased mixture of a sulfurized alkylsalicylate and a sulfurized alkylphenate.
  • the additive provides high synchromesh durability performance and gear protection to a manual transmission gear box.
  • the present invention solves the problem of pitting of metal surfaces in transmissions, especially continuously variable automatic transmissions, by including in the transmission fluid an effective amount of one or more selected compounds which are typically known for use as metal deactivators.
  • the presence of these materials also serves to provide improved (increased) metal-on-metal friction values. These materials are particularly useful in fluids which contain very low amounts of zinc salts of sulfur-containing phosphorus acids.
  • the present invention provides for the use of at least one compound comprising a 5-membered ring containing at least two double bonded nitrogen atoms, to impart improved metal pitting performance to a fluid when said fluid is used in the lubrication of a continuously variable automatic transmission; wherein said fluid comprises an oil of lubricating viscosity and a hydrocarbyl ester of a phosphorous acid and wherein said hydrocarbyl ester of a phosphorous acid comprises a dialkyl hydrogen phosphite.
  • the fluid preferably contains 0 to 0.1 percent by weight of zinc salts of sulfur-containing phosphorus acids.
  • the first component of the present invention is an oil of lubricating viscosity which is generally present in a major amount (i.e. an amount greater than 50% by weight). Generally, the oil of lubricating viscosity is present in an amount of greater than 80% by weight of the composition, typically at least 85%, preferably 90 to 95%. Such oil can be derived from a variety of sources, and includes natural and synthetic lubricating oils and mixtures thereof.
  • the natural oils useful in making the inventive lubricants and functional fluids include animal oils and vegetable oils (e.g., lard oil, castor oil) as well as mineral lubricating oils such as liquid petroleum oils and solvent treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic/naphthenic types which may be further refined by hydrocracking and hydrofinishing processes and are dewaxed. Oils of lubricating viscosity derived from coal or shale are also useful.
  • Useful natural base oils may be those designated by the American Petroleum Institute (API) as Group I, II, or III oils.
  • Group I oils contain ⁇ 90% saturates and/or > 0.03% sulfur and have a viscosity index (VI) of ⁇ 80.
  • Group II oils contain ⁇ 90% saturates, ⁇ 0.03% sulfur, and have a VI ⁇ 80.
  • Group III oils are similar to group II but have a VI ⁇ 120.
  • synthetic oils Upon occasion, highly refined or hydrocracked natural oils have been referred to as "synthetic" oils. More commonly, however, synthetic lubricating oils are understood to include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes); poly(1-hexenes), poly(1-octenes), poly(1-decenes), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); alkylated dipheny
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified such as by esterification or etherification constitute another class of known synthetic lubricating oils that can be used. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having an average molecular weight of about 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, or diethyl ether of polypropylene glycol having a molecular weight of 1000-1500) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3-8 fatty acid esters, or the C 13 Oxo acid diester of tetraethylene glycol.
  • the oils prepared through polymerization of ethylene oxide or propylene oxide the alkyl and aryl
  • esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, or alkenyl malonic acids
  • alcohols e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, or propylene glycol
  • these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecylic acids
  • Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, or tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2pentoxy)disiloxane, poly(methyl) siloxanes, poly-(methylphenyl)siloxanes).
  • synthetic lubricants e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid), polymeric tetrahydrofurans and the like.
  • traction oils are typically synthetic fluids containing a large fraction of highly branched or cycloaliphatic structures, i.e., cyclohexyl rings. Traction oils or traction fluids are described in detail, for example, in U.S. Patents 3,411,369 and 4,704,490.
  • Unrefined, refined, and rerefined oils either natural or synthetic (as well as mixtures of two or more of any of these) of the type disclosed hereinabove can be used in the lubricants of the present invention.
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • the oil of lubricating viscosity is a poly-alpha-olefin (PAO).
  • PAO poly-alpha-olefin
  • the poly-alpha-olefins are derived from monomers having from 4 to 30, or from 4 to 20, or from 6 to 16 carbon atoms.
  • Examples of useful PAOs include those derived from 1-decene. These PAOs may have a viscosity from 2 to 150 cSt.
  • the present invention can be used in transmission fluids which contain only a limited amount of zinc salts of sulfur-containing phosphorus acids.
  • the limited amount is typically 0 to 0.1 percent by weight, more preferably up to 0.05 percent by weight.
  • the fluid is substantially free from such salts, that is, less than 0.01 percent by weight.
  • Typical examples of zinc salts of sulfur-containing phosphorus acids are the zinc dialkyl dithophosphates.
  • Such salts are well known to those skilled in the art of lubricant formulation. They are typically used to impart extreme pressure performance to various lubricating compositions. They are well known to those in the art of lubricant additives. They and their method of preparation are described, for instance in U.S.
  • Metal deactivators are typically nitrogen and/or sulfur containing heterocyclic compounds, such as triazoles, amino-mercaptothiadiazoles, imidazoles, thiazoles, tetrazoles, hydroxyquinolines, oxazolines, imidazolines, thiophenes, indoles, indazoles, quinolines, benzoxazines, dithiols, oxazoles, oxatriazoles, pyridines, piperazines, triazines, and derivatives of any one or more thereof.
  • the materials of interest are typically characterized by the presence in their structure of a 5-membered ring containing at least two double bonded nitrogen atoms.
  • Such molecules may be also characterized by sp 2 hybridization of orbitals within the ring, and a measure of electron delocalization and non-benzene aromatic character within the ring.
  • the materials of this additive component used in this invention are typically one or more compounds selected from the group consisting of aromatic triazoles and mercaptothiadiazoles.
  • the fluid comprises both an aromatic triazole and a mercaptothiadiazole.
  • Aromatic triazoles are materials having the general structure shown here as a substituted benzotriazole. Analogous aromatic materials are also included, which can be based on naphthalene and other aromatic structures.
  • R is hydrogen or a hydrocarbyl group, typically of 1 to 8 carbons, preferably 1 or 2 carbons. When R is methyl, the material is tolyltriazole.
  • Mercaptothiadiazoles are materials generally having the general structure In the structure shown, each R is hydrogen or a hydrocarbyl group having 1 to 30 carbon atoms, preferably, 6 to 15 carbons atoms. R can also represent a sulfur-containing group, R'S-, so that there can be a chain of two sulfur atoms linking the thiadiazole nucleus to the hydrocarbyl group. Such materials are, for instance, dihydrocarbyldithiothiadiazoles.
  • a preferred aromatic triazole is tolyl triazole.
  • Other suitable aromatic triazoles include benzotriazole.
  • a preferred mercaptothiadiazole is 2,5-bis-(tert-nonyldithio)-1,3,4-thiadiazole.
  • Other mercaptothiadiazoles include various derivatives of 2,5-dimercaptothiadiazoles ("DMTD"), including (a) 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazole or 2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazole and mixtures thereof; (b) carboxylic esters of DMTD; (c) condensation products of ⁇ -halogenated aliphatic monocarboxylic acids with DMTD; (d) reaction products of unsaturated cyclic hydrocarbons and unsaturated ketones with DMTD; (e) reaction products of an aldehyde and diaryl amine with DMTD' (f) amine salts of DMTD; (g) dithiocarbamate derivatives of DMTD; (h) reaction products of
  • compositions (a) - (k) are known to those skilled in the art and are described in U.S. Patent 4,612,129 and patent references cited therein.
  • preferred thiadiazoles for use in this invention are those listed in (a), (h), and (k) above.
  • the total amount of the one or more anti-pitting additives described above is generally 0.01 to 0.5 percent by weight of the finished composition. Preferred ranges include 0.03 to 0.1 percent by weight, which is especially preferred when other materials such hydrocarbyl esters of phosphorus acids (described below) are present.
  • One particularly desirable class of materials are those known as dispersants, and in particular, acylated amine dispersants such as succinimide dispersants.
  • Acylated amine dispersants include reaction products of one or more carboxylic acylating agent and one or more amine.
  • the carboxylic acylating agents include C 8-30 fatty acids, C 14-20 isoaliphatic acids, C 18-44 dimer acids, addition dicarboxylic acids, trimer acids, addition tricarboxylic acids, and hydrocarbyl substituted carboxylic acylating agents. Dimer acids are described in U.S. Pat. Nos. 2,482,760, 2,482,761, 2,731,481, 2,793,219, 2,964,545, 2,978,468, 3,157,681, and 3,256,304.
  • the addition carboxylic acylating agents are addition (4+2 and 2+2) products of an unsaturated fatty acid with one or more unsaturated carboxylic reagents, which are described above. These acids are taught in U.S. Pat. No. 2,444,328.
  • the carboxylic acylating agent is a hydrocarbyl substituted carboxylic acylating agent.
  • the hydrocarbyl substituted carboxylic acylating agents are prepared by a reaction of one or more of the above olefins or polyalkenes with one or more of the above unsaturated carboxylic reagents, such as maleic anhydride.
  • the amines can be any of those described elsewhere herein, preferably a polyamine, such as an alkylenepolyamine or a condensed polyamine.
  • a polyamine such as an alkylenepolyamine or a condensed polyamine.
  • Acylated amines, their intermediates and methods for preparing the same are described in U.S. Pat. Nos. 3,219,666; 4,234,435; 4,952,328; 4,938,881; 4,957,649; 4,904,401; and 5,053,152.
  • the preferred materials, succinimide dispersants are prepared by the reaction of an amine and a hydrocarbyl substituted succinic anhydride or the reactive equivalent thereof. These are very well known materials in the art of lubricant formulation and are described in detail in numerous patents, including. U.S. Patents 3,172,892 and 4,234,435.
  • dispersants which may be used include carboxylic esters, Mannich reaction products, hydrocarbyl substituted amines. These materials and methods of their preparation are described in greater detail in PCT publication WO00/70001 and references cited therein.
  • the dispersant can also be a modified dispersant, for example, a borated dispersant.
  • the borated dispersant contains from 0.1% to 5%, or from 0.5% to 4%, or from 0.7% to 3% by weight boron.
  • the borated dispersant is a borated acylated amine, such as a borated succinimide dispersant.
  • Borated dispersants are described in U.S. Pat. Nos. 3,000,916; 3,087,936; 3,254,025; 3,282,955; 3,313,727; 3,491,025; 3,533,945; 3,666,662, 4,925,983 and 5,883,057. Borated dispersants are prepared by reaction of one or more dispersants with one or more boron compounds.
  • Suitable boron compounds for preparing borated dispersants include various forms of boric acid (including metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7 ), boric oxide, boron trioxide, and alkyl borates of the formula (RO) x B(OH) y wherein x is 1 to 3 and y is 0 to 2, the sum of x and y being 3, and where R is an alkyl group containing 1 to 6 carbon atoms.
  • the boron compound is an alkali or mixed alkali metal and alkaline earth metal borate.
  • These metal borates are generally a hydrated particulate metal borate which are known in the art.
  • Alkali metal borates include mixed alkali and alkaline metal borates. These metal borates are available commercially. Representative patents disclosing suitable alkali and alkali metal and alkaline earth metal borates and their methods of manufacture include U.S. patents 3,997,454; 3,819,521; 3,853,772; 3,907,601; 3,997,454; and 4,089,790.
  • the amount of the dispersant in the compositions of the present invention is typically 0 to 5 percent by weight, more commonly 0.5 to 3.0 percent by weight, and preferably 1.5 to 2.5 percent by weight.
  • a phosphorus compound Another common component for transmission fluids is a phosphorus compound, and in the present invention, in particular, an effective amount of a hydrocarbyl ester of a phosphorus acid which comprises a dialkyl hydrogen phosphite will be present. Most phosphorous compounds impart a measure of anti-wear performance to the composition. However, as stated above, the fluids of the present invention may have no or only a limited amount of zinc salts of sulfur-containing phosphorus acids.
  • Dialkyl hydrogen phosphite corresponds to the formula (R 1 X)(R 2 X)P(X) n X m R 3 or a salt thereof, where each X is independently an oxygen atom, n is 0, m is 1, m+n is 1, both of R 1 and R 2 are alkyl and R 3 is hydrogen.
  • Dialkyl hydrogen phosphites are among the phosphorus containing additives which may be used in the transmission fluids of the present invention.
  • a common and preferred example of a dialkyl hydrogen phosphite is di-n-butyl hydrogen phosphite.
  • Dihydrocarbyl hydrogen phosphites can be prepared by techniques well known in the art, and many such phosphites are available commercially.
  • phosphorus-containing materials are phosphites such as dibutyl phosphite (also known as dibutyl hydrogen phosphite). These materials are likewise well known and commercially available
  • phosphorus material is phosphoric acid
  • a typical amount is 0.0085 to 0.17 percent by weight of the composition.
  • the phosphorus material is a hydrocarbyl ester of a phosphorous acid, it will be typically present in amount of 0.025 to 0.5 percent by weight, and preferably 0.005 to 0.25 percent by weight, such as about 0.2 percent.
  • the hydrocarbyl ester of a phosphorous acid can be present in an amount to contribute 0.003 to 0.08 percent by weight phosphorus to the formulated fluid.
  • the transmission fluids of the present invention can contain other conventional components in customary amounts.
  • Other such components include friction modifiers such as metal salts of fatty acids, fatty phosphites, fatty acid amides, fatty epoxides and borated derivatives thereof, fatty amines, glycerol esters and their borated derivatives, alkoxylated fatty amines (including ethoxylated fatty amines such as diethoxylated tallowamine) and their borated derivatives, isostearic acid condensation products of polyamines such as tetraethylene pentamine, such condensates containing amide and imidazoline or imine functional groups, alkyl-substituted imidazolines, sulfurized olefins, sulfurized polyolefins, sulfurized fats, and sulfurized fatty acids.
  • friction modifiers such as metal salts of fatty acids, fatty phosphites, fatty acid amides, fatty epoxides
  • They can also be suspended molybdenum disulfide, dialkyl or diaryl dithiophosphate molybdates or alkyl or dialkyl dithiocarbamate molybdates where the molybdenum is oxydisulfidobridged and chelated with dithiophosphate or dithiocarbamate ligands.
  • detergents such as overbased metal salts
  • viscosity modifiers including hydrocarbon viscosity modifiers such as polybutenes, poly(ethylene/propylene) copolymers, and polymers of styrene with butadiene or isoprene, ester viscosity modifiers such as esters of styrene/maleic anhydride polymers, esters of styrene/maleic anhydride/acrylate terpolymers, and polymethacrylates, and dispersant viscosity modifiers; antioxidants, including hindered phenolic antioxidants, secondary aromatic amine antioxidants, sulfurized phenolic antioxidants, oil-soluble copper compounds, phosphorus-containing antioxidants, organic sulfides, disulfides, and polysulfides.
  • viscosity modifiers including hydrocarbon viscosity modifiers such as polybutenes, poly(ethylene/propylene) copolymers, and polymers of styrene with butadiene or
  • seal swell compositions such as isodecyl sulfolane (that is, isodecyl-3-sulfolanyl ether), which are designed to keep seals pliable.
  • pour point depressants such as alkylnaphthalenes, polymethacrylates, vinyl acetate/fumarate or /maleate copolymers, and styrene/maleate copolymers. All of the foregoing materials are well known and commercially available. They are described in greater detail in PCT publication WO00/70001.
  • composition used in the present invention can be supplied as a fully formulated lubricant or functional fluid, or it can be supplied as a concentrate.
  • the relative amounts of the various components will generally be about the same as in the fully formulated composition, except that the amount of oil of lubricating viscosity will be decreased by an appropriate amount.
  • the absolute percentage amounts of the remaining components will be correspondingly increased.
  • hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • hydrocarbyl groups include:
  • a first base formulation is prepared to which includes 83-86 percent of a 100N base stock, 5.8 percent of a polymethacrylate viscosity modifier, 4.5 percent dispersant(s), 1.0 percent overbased calcium sulfonate detergent, additional diluent oil, and antioxidants and other conventional components at lower levels, each containing the amounts of diluent oil conventionally present in that component.
  • the formulation also contains 0.05% of an alkylated dimercaptothiadiazole and 0.05% of tolyltriazole. To this first base formulation is added the phosphorus additives in the amounts shown in Table I.
  • the formulations are tested by the FZG pitting test.
  • a Strama TM FZG Gear Oil Test Rig and "C" profile gears 14 mm wide are used. After a break-in period, the test is run with a loading of 453 Nm (334 lb. ft.) on the wheel at 1440 r.p.m. and 90°C.
  • the gears, lubricated with the 1.25 L of test fluid are inspected and rated every 24 hours until failure or 300 hours, whichever first occurs. Failure is define as 4% damage of a single tooth or 1% of the total load-carrying surface. In the results, higher numbers (number of hours) are preferred. The results are shown in Table I.
  • a second base formulation is prepared to which includes 83-86 percent of a 100N base stock, 6.3 percent of a polymethacrylate viscosity modifier, 3.1 percent dispersant(s), 1.8 percent overbased calcium sulfonate detergent, 0.2 percent dibutylphosphite, additional diluent oil, and antioxidants and other conventional components at low levels, each containing the amounts of diluent oil conventionally present in that component, including 0.05 percent of a zinc dialkyldithiophosphate.
  • the formulation also contains an alkylated dimercaptothiadiazole and/or a tolyltriazole in the amounts set forth in Table II..

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (12)

  1. Verwendung wenigstens einer Verbindung, welche einen fünfgliedrigen Ring, der wenigstens zwei doppelt gebundene Stickstoffatome enthält, umfaßt, um einer Flüssigkeit eine verbesserte Leistung gegen Metallochfraß zu verleihen, wenn die Flüssigkeit zum Schmieren eines Getriebes verwendet wird,
    wobei die Flüssigkeit ein Öl mit schmierender Viskosität und einen Hydrocarbylester einer Phosphonsäure umfaßt und wobei der Hydrocarbylester einer Phosphonsäure ein Dialkylhydrogenphosphit umfaßt.
  2. Verwendung nach Anspruch 1, wobei die Verbindung unter aromatischen Triazolen und Mercaptothiadiazolen ausgewählt ist.
  3. Verwendung nach Anspruch 1 oder Anspruch 2, wobei die Flüssigkeit sowohl ein aromatisches Triazol als auch ein Mercaptothiadiazol umfaßt.
  4. Verwendung nach Anspruch 2 oder Anspruch 3, wobei das aromatische Triazol Tolyltriazol umfaßt und das Mercaptothiadiazol 2,5-bis-(tert-Nonyldithio)-1,3,4-thiadiazol umfaßt.
  5. Verwendung nach einem der vorangegangenen Ansprüche, wobei die Menge der Verbindung 0,02 bis 0,5 Gewichtsprozent beträgt.
  6. Verwendung nach einem der vorangegangenen Ansprüche, wobei die Flüssigkeit weiterhin wenigstens ein Succinimiddispergiermittel umfaßt.
  7. Verwendung nach Anspruch 6, wobei das Succinimiddispegiermittel ein boriertes Dispergiermittel ist.
  8. Verwendung nach einem der vorangegangenen Ansprüche, wobei die Flüssigkeit weiterhin eine Phosphonsäure umfaßt.
  9. Verwendung nach einem der vorangegangenen Ansprüche, wobei die Flüssigkeit weiterhin 0 bis 0,1 Gewichtsprozent eines Zinksalzes einer Schwefel enthaltenden Phosphonsäure umfaßt.
  10. Verwendung nach einem der vorangegangenen Ansprüche, wobei das Getriebe ein stufenloses Automatikgetriebe ist.
  11. Verwendung nach Anspruch 10, wobei das stufenlose Automatikgetriebe ein Getriebe mit Riemenantrieb ist.
  12. Verwendung nach einem der vorangegangenen Ansprüche, wobei das Dialkylhydrogenphosphit Dibutylhydrogenphosphit ist.
EP02257642A 2001-11-06 2002-11-05 Flüssigkeit für Getriebe mit veringerter Rostfrasskorrosion Revoked EP1308496B1 (de)

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US33293201A 2001-11-06 2001-11-06
US332932 2001-11-06

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EP1308496B1 true EP1308496B1 (de) 2006-06-14

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Cited By (10)

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US7683013B2 (en) 2005-06-07 2010-03-23 Exxonmobil Research And Engineering Company Base stock lubricant blends for enhanced micropitting protection
US8247358B2 (en) 2008-10-03 2012-08-21 Exxonmobil Research And Engineering Company HVI-PAO bi-modal lubricant compositions
US8394746B2 (en) 2008-08-22 2013-03-12 Exxonmobil Research And Engineering Company Low sulfur and low metal additive formulations for high performance industrial oils
US8535514B2 (en) 2006-06-06 2013-09-17 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst PAO novel base stock lubricant blends
US8598103B2 (en) 2010-02-01 2013-12-03 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
US8642523B2 (en) 2010-02-01 2014-02-04 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8716201B2 (en) 2009-10-02 2014-05-06 Exxonmobil Research And Engineering Company Alkylated naphtylene base stock lubricant formulations
US8728999B2 (en) 2010-02-01 2014-05-20 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8748362B2 (en) 2010-02-01 2014-06-10 Exxonmobile Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
US8759267B2 (en) 2010-02-01 2014-06-24 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient

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Publication number Priority date Publication date Assignee Title
WO2006115666A1 (en) * 2005-04-22 2006-11-02 Exxonmobil Chemical Patents Inc. Improved corrosion protection for lubricants
JP5030402B2 (ja) * 2005-08-15 2012-09-19 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物
CN101517046B (zh) 2006-07-27 2013-11-13 卢布里佐尔公司 润滑方法及其润滑组合物
EP3981863A1 (de) * 2013-05-14 2022-04-13 The Lubrizol Corporation Schmiermittelzusammensetzung und verfahren zum schmieren eines getriebes
FR3097875B1 (fr) * 2019-06-28 2022-03-04 Total Marketing Services Composition lubrifiante pour prévenir la corrosion et/ou la tribocorrosion des pièces métalliques dans un moteur

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CA1169847A (en) * 1980-01-24 1984-06-26 Carl A. Eggers Hydraulic fluid, hydraulic equipment containing this fluid and a concentrate of this fluid
JPS6084394A (ja) * 1983-09-19 1985-05-13 Idemitsu Kosan Co Ltd 疲労寿命改良潤滑剤
US5759965A (en) * 1995-10-18 1998-06-02 The Lubrizol Corporation Antiwear enhancing composition for lubricants and functional fluids
EP0976813B1 (de) * 1998-07-31 2003-12-10 Chevron Oronite S.A. Gegen Hydrolyse beständiges Borat enthaltendes Handschaltgetriebe-Schmieröladditiv zum Erhöhen der Dauerhaftigkeit von Synchrongetrieben
US6034040A (en) * 1998-08-03 2000-03-07 Ethyl Corporation Lubricating oil formulations
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US7683013B2 (en) 2005-06-07 2010-03-23 Exxonmobil Research And Engineering Company Base stock lubricant blends for enhanced micropitting protection
US8535514B2 (en) 2006-06-06 2013-09-17 Exxonmobil Research And Engineering Company High viscosity metallocene catalyst PAO novel base stock lubricant blends
US8394746B2 (en) 2008-08-22 2013-03-12 Exxonmobil Research And Engineering Company Low sulfur and low metal additive formulations for high performance industrial oils
US8247358B2 (en) 2008-10-03 2012-08-21 Exxonmobil Research And Engineering Company HVI-PAO bi-modal lubricant compositions
US8476205B2 (en) 2008-10-03 2013-07-02 Exxonmobil Research And Engineering Company Chromium HVI-PAO bi-modal lubricant compositions
US8716201B2 (en) 2009-10-02 2014-05-06 Exxonmobil Research And Engineering Company Alkylated naphtylene base stock lubricant formulations
US8598103B2 (en) 2010-02-01 2013-12-03 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
US8642523B2 (en) 2010-02-01 2014-02-04 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8728999B2 (en) 2010-02-01 2014-05-20 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
US8748362B2 (en) 2010-02-01 2014-06-10 Exxonmobile Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
US8759267B2 (en) 2010-02-01 2014-06-24 Exxonmobil Research And Engineering Company Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient

Also Published As

Publication number Publication date
DE60212292D1 (de) 2006-07-27
EP1308496A2 (de) 2003-05-07
DE60212292T2 (de) 2007-05-31
EP1308496A3 (de) 2003-05-28
ATE329989T1 (de) 2006-07-15

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